Azo dyestuffs

ABSTRACT

Fiber reactive dyestuffs for use on cellulose containing textile materials having the formula   WHEREIN F is the radical of an organic dyestuff, A is a five- or six-membered isocyclic or heterocyclic ring, X is hydrogen or an organic substituent, Y is hydrogen, halogen or an organic radical, &#39;&#39;&#39;&#39;halogen&#39;&#39;&#39;&#39; is a halogen atom, m a whole number and n a whole number from 1 to 3.

United States Paten Siegel et a1. a 1 May 30, 1972 [54] AZO DYESTUFFS Pn'mm'y Examiner-Charles B. Parker [72] Inventors: Edgar Siege], Leverkusen; Klaus m, fifg fgfzzggigg gs Papuga Cologne-Stammheim, both of Germany y [73] Assignee: Farbeniabriken Bayer Aktiengesellschaft,

Leverkusen, Germany [57] ABSTRACT Filedi 1968 Fiber reactive dyestuffs for use on cellulose containing textile 2 App] 775 554 rnaterials having the formula Related U.S.-App1lcat1on Data Continuation of Ser. No, 171,269, Feb. 5, 1962, abancloned.

References Cited FOREIGN PATENTS 0R APPLICATIONS 7 1929 Great Britain 260/154 C-halogen wherein F is the radical of an organic dyestuff, A is a fiveor six-membered isocyclic or heterocyclic ring, X is hydrogen or an organic substituent, Y is hydrogen, halogen or an organic radical, halogen is a halogen atom, in a whole number and n a whole numlger from I to 3.

16 Claims, No Drawings A nYFsTUFrs CROSS REFERENCE TO RELATED APPLICATION This application is a continuation of application, Ser. No. l 71,269 filed Feb. 5, 1962 and now abandoned.

The present invention relates to novel and valuable dyestuffs; more particularly it relates to dyestuffs of the general formula C-halogen In this formula F denotes the radical of an organic dyestufi, A means a fiveor six-membered isocyclic or heterocyclic ring, X denotes hydrogen or an organic substituent, Y means hydrogen, halogen or an organic radical, halogen" means a halogen atom, m a whole number and n a whole number from I to 3.

It is an object of this invention to provide new valuable dyestuffs and processes for their manufacture; another object is the provision of new fiber reactive dyestuffs which are particularly useful for the dyeing and printing of cellulose-containing textile materials. A further object is the provision of new dyestufis which exhibit outstanding wet fastness properties when dyed or printed on OH-group containing materials according to methods known for fiber reactive dyestuffs. Still another object is the provision of a method for dyeing textile materials, particularly cellulose-containing textile fibers with the novel fiber reactive dyestuffs. It is also an object of the invention to provide textile materials, particularly cellulose-containing fibers which are dyed and printed very fast to wet processing and which posses excellent general fastness properties. Other objects will become evident from the following description.

The dyestuffs of formula (I) may belong to a great variety of classes, for example to the series of metal-free or metal-containing monoor polyazo dyestufis, metal-free or metal-containing azaporphine dyestuffs, preferably phthalocyanine dyestuffs, anthraquinone, nitro, oxan'ne, dioxazine, triphenylmethane, azomethine, benzanthrone and dibenzanthrone dyestuffs as well as polycyclic condensation compounds of the latter.

Preferred dyestuffs of the the fonnula present invention correspond to N F T-O C Hal I H l a N m wherein F stands for the radial of a metal-free sulfonic acid group-containing azo dyestuff, the

group being bonded thereto directly through a nuclear carbon atom, R is a member selected from the group consisting of hydrogen and lower alkyl, m is an integer from 1 to 2 and Hal is a member selected from the group consisting of Cl and Br.

In the dyestufis of the general formula (I the radical can be linked with the dyestuff molecule either directly or via optional bridge members. As bridge members there are to be mentioned for example sulfonamide, sulfonylamino, carbonamide, carbonylamino, alkylene, aralkylene, arylene, amino, alkylenearnino, aralkyleneamino, arylenearnino groups, amino groups which may be substituted by alkyl, aryl, aralkyl or acyl groups, bisacylimide groups such as bis-sulfonylamide groups and sulfonyl-carboxylimide or sulfonyl-triazinyl or -pyrimidinyl groups, further urea and urethane groupings, heterocyclic ring systems such as triazinylamino and pyrimidinylamino radicals which may also exhibit reactive halogen atoms, as well as oxygen and sulfur atoms and the azo grouping. Of particular importance are those dyestuffs in which the residue (ll) is linked with the dyestuff via an optionally at the nitrogen atom substituted sulfonamide or carbonamide group, the

group of which is bound to the nucleus A.

The bridge member may connect the radical F with the ring system A either via two or via three linking positions whereby in the latter case, for instance a fiveor six-membered ring which is condensed with the nucleus A and which contains exchangeable halogen atoms (e. g. a compound of formula IV) may be reacted with amino group-containing dyestuffs.

As substituents X there are to be considered inter alia: optionally substituted alkyl, aralkyl and aryl radicals, sulfonic acid, carboxylic acid, halogen substituents, such as chlorine and bromine substituents, further nitro, hydroxy, alkoxy cyano, sulfone and optionally substituted sulfonamide groups, acid ester groupings such as sulfonic acid and carboxylic acid ester groups and the like. Among the halogen substituents in the pyrazine radical, chlorine and bromine substituents are of special interest. In the case where Y represents an organic radical, the latter may be of any desired type, for example an optionally substituted alkyl group, an alkylamino-, aralkylamino-, arylaminoor acylamino group, an alkylor a'rylsulfonyl-amino group, further radicals of aliphatic and arornatic hydroxy or mercapto compounds. Of course, Y may also stand for the radical of a colored component, that is to say of any desired dyestufi'.

The new dyestuffs of the formula (I) may be water-soluble or also barely or even insoluble in water, depending on the type of their substituents. The radical F may contain the substituents customary for the dyestufis present in each case, such as sulfonic acid, carboxylic acid, optionally substituted sulfonamide, sulfone, alkylamino, aralkylamino, arylamino, acylamino,nitro, cyano, halogeno, hydroxy, alkoxy, azo groupings and the like. The dyestuffs may moreover contain further groupings capable of fixation such as monoor dihalotriazinylamino, mono-, dior tri-halopyridinylamino, halopyrimidinylamino, esterified sulfonic acid hydroxy alkylamide and esterified hydroxy alkylsulfone groups, vinyl sulfone, sulfofluoride, haloalkylamino and haloacylamino, epoxide, urethane, unsaturated haloalkylurethane, isocyanate, isothiocyanate groups and the like.

The new dyestuffs can be built up according to a variety of principles of preparation. For example, dyestuffs or dyestuff intermediates containing amino or amide groups and having a reactive hydrogen atom at the amine or amide nitrogen, can be reacted with compounds of the general formula (II) which contain a reactive grouping, for example a carboxylic acid halide, sulfonic acid halide or isocyanate grouping, in the fiveor six-membered aromatic or heterocyclic nucleus A, and if dyestufi intermediates are used, the latter can be converted in a suitable manner into the desired final dyestufis. In the opposite case, dyestuffs or dyestuff intermediates which contain reactive groupings, for example in the form of sulfonic acid halide, carboxylic acid halide, urethane, ester, haloalkyl and similar groupings, can be reacted with those compounds of the formula (ll) which contain in the aromatic or heterocyclic nucleus A an amino or amide group with replaceable hydrogen and, insofar as dyestuff intermediates are used, the

latter can again be converted into the desired final dyestufis. In the case of production of azo group-containing dyestuffs, it is also possible to use such compounds of the general formula (ll) which are substituted in the nucleus A by a diazotizable amino group, to diazotize these components and to couple them in conventional manner with any desired coupling component and using them in this way for building up monoor poly-azo dyestuffs.

When principles other than those described above are applied, for example with the formation of oxygen, sulfur or acid ester groupings, a number of further dyestuifs of the general formula (I) are obtained according to equally well-known methods. Dyestuffs in which the radical of the formula (ll) is directly linked with F can be built up in the series of azo compounds for example by diazotizing an aminoaryl compound which contains the aryl nucleus directly linked with the fiveor six-membered nucleus A of the compound of the general formula (ll) via a carbon-carbon bond, and possibly coupling with azo components.

Depending upon the number of appropriate groupings in the dyestufi radical or dyestuff intermediates to be considered for the conversion, one or more groupings of the general formula ll) can be incorporated in the dyestuffs. In the majority of cases, the number m will not exceed 4, but it is also possible to synthesize dyestuffs with more than 4, for example with up to 8 groupings of the formula (ll), especially those of high molecular structure.

Some of the intermediate products of the formula (ii) are known from literature (c.f. e.g. Angewandte Chemie U960], 72, page 973). From these some of the products suitable for the preparation of the final dyestuffs or dyestuff intermediates can be synthesized by subsequent introduction of the appropriate groupings, for example by sulfochlorination. in general, it is however advantageous to introduce the desired groups, for example carboxylic acid or carboxylic acid chloride, nitro, amino, amido or acylamino groups, into the nucleus A of the o-arylene-diamino compound already before the ring closure to form the pyrazine ring.

In this case, the process starts, for example, from a 1,2- diaminobenzoic acid, -sulfonic acid or a triaminobenzene compound (with at least two o-positioned amino groups) or from a derivative which is acylated or substituted at an amino group which shall not take part in ring closure, this compound is reacted with oxalic acid with the formation of a quinoxaline ring and the free hydroxy groups are converted into halogen substituents, if desired after conversion of the substituent contained in the nucleus A, in the case of a nitro group, for example, after reduction. Sometimes it is also possible to combine the conversion of the hydroxyl groups into halogen atoms in.

one step with a possibly desirable conversion of a substituent contained in the nucleus A, for example an amino group, for example by converting the amino group-containing dihydroxy compound with phosgene in the presence of dimethylformamide into the corresponding isocyanate group-containing dihalogeno compound. In the intermediate products or after formation of the dyestuffs of the formula halogen the aminoanthraquinone series with nuclear-positioned and/or externally linked amino groups, by the reaction with compounds of the formula (ll) which contain in the fiveor sixmembered nucleus A a reactive grouping, for example a car boxylic acid chloride, sulfonic acid chloride, isocyante, urethane, halotriazinylamino, halopyrimidinylamino or also a dichloroquinoxalinoyl or dichloroquinoxalinoyl-methylene group. Likewise, an amino group-containing dyestufl or dyestuif intermediate can be combined in a simple manner with a dichloroquinoxaline containing an amino group in the nucleus A, by means of polyfunctional acylating agents, for example by reacting the amino group-containing starting components with phosgene, aliphatic or aromatic dicarboxylic acid halides, cyanuric halides or di-, trior tetrahalopyrimidine.

A special case of linking the radical of the formula (Il) with the dyestuff is attained by starting from a dihaloquinoxaline derivative with a condensed dihalopyrazine ring, having for example the formula N N out U 101 Cl \N/ Cl and condensing in this compound at least one of the reactive halogen atoms with an amino group-containing dyestuff or dyestuff intermediate.

it will be understood that a great number of other starting components can be used in the preparation of the novel dyestuffs.

The new dyestuffs are valuable products which are excellently suitable for various purposes of application. As watersoluble compounds they are of special interest for the dyeing 0f nitrogen-containing and hydroxyl group-containing textile materials, especially of native and regenerated cellulose, wool, silk, synthetic polyamide and polyurethane fibers. On account of the reactive halogen substituents in the pyrazine radical, the products are particularly suitable as reactive dyestufis for the dyeing of cellulose materials according to the techniques known for this purpose,

For the dyeing of natural and regenerated cellulose the dyestuffs are preferably used in an aqueous solution which may be treated with substances having an alkaline reaction such as alkali metal hydroxide or alkali metal carbonate or with compounds convertivle into substances of alkaline reaction such as alkali metal bicarbonate. Further auxiliaries may be added to the solution but they should not react with the dyestuffs in an undesirable manner. Additives of this kind are for example surface-active substances such as alkyl sulfates, substances preventing migration of the dyestuff, dyeing adjuvants such as urea which is to improve the solubility and fixation of the dyestuff, or inert thickening agents such as oil-inwater emulsion, tragacanth, starch, alginate or methyl cellulose.

The solutions or pastes thus prepared are applied to the material to be colored, for example by padding on the foulard (short bath) or by printing, and subsequently heated to an elevated temperature, preferably 40 C., for some time. Heating can be effected in the hot flue, in a steaming apparatus, on heated rollers or by introduction into heated concentrated salt baths.

When using a padding or dyeing liquor without alkali the colored dry material is subsequently passed through an alkaline solution to which sodium chloride or Glaubers salt are added. The addition of salt prevents migration of the dyestuff from the fiber.

The material to be dyed can also be pre-treated with one of the aforesaid acid-binding agents, subsequently treated with a solution or paste of the dyestuff and, finally, fixed at an elevated temperature as described above.

In the so-called cold pad batch process, the subsequent heating of the padded fabric can be dispensed with by storing the fabric at room temperature for 4 hours. In this process sodium carbonate solution is preferably used as alkali.

For dyeing from a long liquor, the material is introduced into an aqueous solution of the dyestuff (goods-to-liquor ratio 1 5 to 1 40) at room temperature and dyed, if desired while raising the temperature up to 85 C. for 40 90 minutes with the addition in portions of salt, for example sodium sulfate, and subsequently of alkaline substances for example sodium phosphates, sodium carbonate or alkalies.

After fixation the dyed material is rinsed hot and, if required, finally soaped, thereby removing insufiiciently fixed dyestufi residues. Dyeings of excellent fastness to wet processing are thus obtained.

For printing materials containing hydroxyl groups, a printing paste is used consisting of the dyestuff solution, a thickening agent, such as sodium alginate, and a compound having alkaline reaction or dissociating alkali on heating, such as sodium carbonate, sodium phosphate, potassium carbonate, potassium acetate or sodium and potassium bicarbonate, the printed material is rinsed and, if desired, finally soaped.

When the dyestuffs, in particular azo dyestuffs, contain groupings forming metal complexes, the fastness properties of the dyeings and prints can in many cases be improved by an after-treatment with metal-yielding agents such as copper salts, for example copper sulfate; chromium, cobalt and nickel salts such as chromium acetate, cobalt sulfate or nickel sulfate.

Textile materials containing amide groups such as wool, silk, synthetic polyamide and polyurethane fibers are in general dyed in the acidic to neutral range according to the dyeing methods conventionally used for this purpose whereby a final increase of the pH value of the dyebath to, for example pH 6.5 to 8.5 is sometimes of advantage.

The dyestuffs are applied to a synthetic polyamide fabric, for example, as solutions or, preferably, in dispersed form and subsequently after-treated together with acid-binding agents in preferably small amounts, such as sodium carbonate. Especially advantageous results are achieved with dyestuffs which are insoluble or barely soluble in water. These are worked up according to conventional techniques and with the addition of known auxiliaries into a dyestutf dispersion and used as such in the dyeor padding-liquor or in a printing paste. Auxiliaries suitable for this application are inter alia compounds preventing the migration of the dyestufi on the fiber such as cellulose ether,alkali metal chlorides and sulfates; wetting agents such as condensation products from ethylene oxide and fatty alcohols or phenols, sulfonated fatty alcohols, solvents such as thiodiglycol; further thickeners such as starch, tragacanth, alginate thickening, gum arabic etc.

After-treatment of the dyeings impregnations and prints obtained on polyamide fiber fabrics is preferably carried out at a temperature of 50 1 10 C. for 5 60 minutes. In the case where the dyestuffs employed contain groupings forming metal complexes, the fastness properties of the dyeings will sometimes be improved by treating the dyeings with metalyielding agents such as copper salts, for example copper sulfate, or chromium, cobalt and nickel salts such as chromium acetate, cobalt sulfate or nickel sulfate.

The dyeings and prints obtainable with the new dyestuffs on cellulosic material are, in general, distinguished by good to very good fastness properties, especially by excellent fastness to wet processing, such as to washing to boiling soda and furthermore to water, to rubbing and brushing, to light and in some instances to chlorine and to peroxide. The dyeings and prints on woollen fabrics possess very good fastness to washing, milling, sea-water, hot water and to light. Dyeings and prints on synthetic polyamide fabrics are distinguished by very good fastness to water, washing and light whereas dyeings and prints on synthetic polyester materials, particularly on polyethylene terephthalate, exhibit good fastness to sublimation, to washing and to light.

The following examples are given for the purpose of illustrating the invention, the parts being parts by weight if not otherwise stated.

EXAMPLE 1 Twenty-eight parts by volume of concentrated hydrochloric acid are added to a solution of 34.7 parts of 2- aminonaphthalene-4,8-disulfonic acid sodium salt and 7 pans of sodium nitrite in 300 parts of water while cooling with ice, and the mixture is stirred at 0-l0 C. for one-half hour. After removal of excess nitrous acid, l0.7 parts of 3-aminotoluene dissolved in 10 parts by volume of concentrated hydrochloric acid and 150 parts of water are added and coupling is completed by adjusting the hydrochloric acid solution to pH 3-5. The resultant aminoazo dyestuff is salted out, filtered off with suction, washed and then re-dissolved in 700 parts of water at pH 7 with the addition of sodium hydroxide solution. The aqueous solution is then treated with 26.5 parts of 2,3- dichloroquinoxaline-6-earboxylic acid chloride (m.p.l 16 C., b.p. 144 C./0.05 mm Hg) dissolved in 100 parts of benzene and vigorously stirred. By the reaction now setting in the mixture warms up to 3540 C.; the hydrochloric acid set free is neutralized with sodium carbonate solution until a free amino group can no longer be detected. The resulting dyestuff of the formula is salted out with parts of sodium chloride, pressed off, washed and dried at 40-50 C. under vacuum. It is a yellow powder which dissolves in water with a yellow color.

When a cellulose fabric is printed with a printing paste containing per kilogram 15 grams of the dyestuff, g of urea, 300 ml of water, 500 g of alginate thickening (60 g of sodium alginate per kg of thickening), 2 g of sodium hydroxide and 10 g of sodium carbonate, and made up to 1 kg with water, then dried, steamed at C. for 8 minutes,'rinsed with hot water and boiled with soap, an intense reddish yellow print of good fastness to washing and light is obtained.

EXAMPLE 2 When 46 parts of the amino-monoazo dyestuff of Example 1 are stirred in an aqueous solution with a solution of 24 parts of 2,3-dichloroquinoxaline--isocyanate in benzene at pH 77.5 (phosphate buffer), until a free amino group can no longer be detected, there is obtained after salting out, pressing off and with which a cotton fabric can be dyed from a long bath in reddish yellow shades fast to washing and light, in the following manner:

Fifty g of cotton skein are dyed in 1 liter of a dyebath containing 1.5 of the above dyestuff by raising the temperature from 20 to 80 C. within 30 minutes while adding a total of 50 g of sodium chloride in several portions, subsequently adding 20 g of trisodium phosphate and treating at this temperature for 60 minutes. After rinsing, boiling with soap and drying there is obtained a reddish yellow dyeing of good fastness to wet processing, rubbing and light.

EXAMPLE 3 Forty-six parts of the monoazo dyestuff obtained analogously to the instructions of Example 1 by coupling diazotized 2-aminonaphthalene-4,8-disulfonic acid with 3- O Na I on,

| N N=N- No2s I01 H 01 I N/ S O Na is salted out, filtered off with suction, washed and dried.

A cotton fabric is impregnated with a solution of 2025 C. containing per liter of liquor 20 g of the above dyestufl and 0.5 g of a non-ionogenic wetting agent (e.g. a polyethoxylated oleyl alcohol) as well as 150 g of urea and g of sodium bicarbonate. Subsequently the fabric is squeezed off between two rubber rollers to a moisture content of about 100 percent. After intermediate drying at 50-60 C., the fabric is heated to 140 C. for 10 minutes and the dyeing thus obtained thoroughly rinsed with hot water and treated at the boil for minutes with a solution containing per liter 5 g of Marseille soap and 2 g of sodium carbonate. After rinsing and drying, there is obtained an intense reddish yellow dyeing of good fastness to wet processing, rubbing and light.

In the following table there are listed the diazo components, coupling components and reactive components which can be linked with the amino group, from which components dyestuffs can be synthesized in analogy to the instructions of Examples 1 3; their shades obtained according to one of the methods of application described above are likewise listed in the Table.

Abbreviations for the reactive components:

A=2,3-dichlorquinoxaline-ti-carboxylic acid chloride B =2,3-dichlorquinoxaline-G-isocyanatc C =2,3-dichlorquinoxaline-fi-sulphochlond 'tained crystallizes in yellowish small needles and after dilution with 600 parts of water and addition of 12 parts of sodium carbonate, it is coupled at 5-l0 C. with 17.5 parts of diazotized Z-aminobenzene-sulfonic acid dissolved in 200 parts of water. The dyestuff formed at a final pH of about 7 and having the formula N s 031% H v -0 C [ei N=N c1 N803 S s OmNit is salted out with 100 parts of sodium chloride, filtered off with suction, washed and dried at -50 C. in a vacuum. The dyestuff forms small red needles which have a metallic lustre and easily dissolve in water with a red color.

By dyeing or printing a fabric of cotton or regenerated cellulose with this dyestufi according to one of the methods described in Examples l-3, there are obtained clear bluish red dyeings and prints of good fastness to wet processing, rubbing and light.

Similar results are also obtained by proceeding according to the method of application of Example 2, but carrying out the addition of salt and the l-hour after-treatment with trisodium phosphate not at C., but at room temperature (20 30 C.). This is also true of the method of Example 3 according to which there are likewise obtainable red dyeings with the fastness properties mentioned above when using 20 g of sodium carbonate or 10 ml of sodium hydroxide solution, 38B., instead of the 15 g of sodium bicarbonate there employed, and storing the cellulose fabric squeezed to a moisture content of percent at room temperature for 20 hours instead of intermediately drying and heating to C.

In the following table there are given the shades of further dyestuffs which are synthesized from the below listed diazo Reactive Example compo- No. Diazo components p g components nents Shade z-ammonaphthaline-4-8-disulphonic acid.. 11mgno-2-methuxy-5-methylbenzol A Y ll O 0 B De, l-auiiinonaphthaleneBfi-disulphonic acid 0 Do. 2-aminonaphthalene-5,7-disulp Do. do Do. 2-aminonaphthalene-6,8-disulphonic ac Do. Do. 4-aminoazobenZeIte-B,4'-diSulph0nic acid Brown.

allow. 1-a1ninobenzene4-st1lph0nic acid 1-aminonaphthalene-B-sulphonic acid do B D 2-(3'- ulpho-4'-aminophenyl)-6-methy1-benzthiazole-7-sulphonic acid do A Yellow, 2-3minonaphthalene-4,8-disulphonic acid 1-methylamin0-3-methoxyhenzene 0 D do 1-am1no-3-acetylamiriobenzene A Do. do Aniline A D EXAMPLE l8 Into a solution of 36.5 parts of the sodium salt of l-amino-8- hydroxynaphthalene-3,fi-disulfonic acid in 100 parts of water there are introduced with good stirring 26.5 parts of finely powdered 2,3-dichloroquinoxaline-6-carboxylic acid chloride, and the mixture is stirred while continuously neutralizing the hydrochloric acid set free to pH 6-7, until a free amino group can no longer be detected. The dyestuff intermediate thus ob- 7 55 components, coupling components and reactive components capable of being linked with free amino groups in the coupling components, analogously to the instructions of Example l8, or also by reaction of the corresponding arninoazo dyestuffs with the reactive components; the fiber reactive dyestuffs can be dyed or printed on cellulose-containing materials according to one of the processes described above:

Abbreviations for the reactive components as in table to Example 3 Reactive Example comp, N0. Diazo components Coupling components nents Shade 19 l-aminobenzene-Z-sulphonic acid I-aminQ-MwdmXyua htha1ene-3,s-d 1 h 13 Belt 20 inob nzoylamino)-8-hydmxyna mha1ene-3, A

disnlphonic acid. 21 d0 d B 22 l-amino2-carboxybcnzene-4-sulphonic acid- A 23 1-amino-4-methylbenzene-z-sulphonic acid A 24 l-amino3-acetylaminobenzene-G-sulphonic acid B D0 25 1-amino3-(2'-[4-sulphophenylamino]4-chlortriazine- A 1',3,5-yl-6") aminobenzene-B-snlphonic acid. 26 l-aininobcnzcne-2-sulphonic acid Q-amlno-S-hydroxynaphthalene-7-sulphoni a id 0 26a l-mnino-B-(2-[4"-sulphophenylamino]-4-methylam1np- H..- o

triazinc-l,3,5-yl-6')-mnino-benzene-G-sulphonic acid. 2T". l 2llllillObOllZtllU-Z-SlllpllOlliC acid met ylam1no-5-hydroxynaphthalene-7-sul h ni id (3 L l-mni1iod-nectyI-mnino-lS-sulplionicacid" .d0 C scarlet 39m Laulln0-541ydroxynaphthalene-7-sulphonic acid A Do.

EXAMPLE 30 into a solution of 2i parts of the sodium salt of 1,3- diaminobenzene-G-sulfonic acid in 100 parts of water there are introduced with good stirring 26.5 parts of finely powdered 2,3-dichloroquinoxaline-G-carboxylic acid chloride and the mixture is stirred at 20-40 C. while continuously neutralizing the hydrochloric acid set free to pH 6-7, until a sample, after diazotization and coupling with l-hydroxynaphthalene-4-sulfonic acid, shows a clear yellowish red color. After the addition of ice, the resultant dyestuff intermediate is directly diazotized with 7 parts of sodium nitrite and 28 parts of concentrated hydrochloric acid and subsequently combined with a solution of 47 parts of the sodium salt of l-benzoylamino-S-hydroxynaphthalene-3,6-disulfonic acid and 12 parts of sodium carbonate in 200 parts of water, whereupon coupling takes place to give the dyestufi of the formula S O Na HO IFIH-OC-Culh N=N 2 c1 iN which is salted out, filtered off with suction, washed and dried 2 under vacuum at 40-50 C. The dyestuff readily dissolves in water with a red color and yields clear bluish red dyeings and prints on cellulose material according to one of the processes described above.

When a fabric of synthetic polyamide fibers is dyed by boil- 3 ing,in a goods-to-liquor ratio of l:30,in a bath containing 2 percent of the dyestuff mentioned above (referred to the weight of the goods) and 2 percent of formic acid (referred to the weight of the material to be dyed), a clear bluish red dye- NaO S l0 hydroxy-Z-aminobenzene-4-sulfonic acid and coupling with 2- amino-5-hydroxynaphthalene-7-sulfonic acid in waterpyridine in the presence of sodium carbonate and subsequent treatment with a copper-yielding agent, said dyestuff having the formula Cu (I) Niims N11- SO Na groups can no longer be detected, the resultant reactive dyestuff of the formula is salted out, pressed off, washed'and dried under vacuum at 40-'50 C. Fabrics of cellulose materials can be dyed or S gf fi f fi Y zg i g is g g l n g 231 printed with this dyestuff in ruby shades fast to wet processing, The 0 owing 6 gives e s a e P v o rubbing and light according to one of the processes mentioned coupling medium of dyestufis which can be produced above analogously to the instructions of Example 30 from a diazo component containing a further, preferably acylatable amino in the followmg table there are listed h he vy metal comgroup,acoupling component andareactive component which plexes of further am noazo dyestuffs and the reactive comcan be linked with the diazo component. The processes men- Ponents linked Wlth the ammo S las the Shades f tioned above can be used for dyeing and printing cellulose these dyestuffs on cellulose materials. The production of the materials with these dyestuffs. aminoazo dyestufls, their metal complexes and their reaction Abbreviations for the reactive components as in the table of with the reactive components can be carried out analogously Example 3. to the instructions of Example 47.

Reactive pl[ of Example compocoupling No. Diuzocomponents Coupling components IIIJIlS medium Shade 31 1,3-(1iumi1iohcnzcuc-l-sulphonicacid... 2-aminmiaplitlialone-5,7-disulphonic acid 4-5 Orange 1 2amin01iaplitllalcnc-3,6-disulphonic acid 4-5 D Z-aminonaphtlialcnc-G-sulphonic ucid 4-5 Do. .Z-N-mctllylamino-8-hydr0xynaphlhaluncfi-sulphon acid A 4-5 D0. 1-(2,4-dichlortriuzinc-l,8,5-yl-6-amino)-8-hydroxynaplitha- C 7-8 Red,

lcuc-3,6-disulphonic acid. 1-(2,4-dihydroxytriazinc-l',3,5,yl6-umino)-8-l1ydrox y B 7-8 D0.

uaplitlutlcnc-3,6disulphonic acid. 37 c1o 1-(2,3-dichl0rquinoxzili1myl-6-mnil10)-8-llydr0xy1iaplithalonc- A 7-8 Do,

3,6-disulph0nic acid. 38 do 2-hydr0xyuupl1thulcnc-3,6-disulphonic acid A Sc rlet, 3 d0 l-acctylumin0-8-liydrcxynuphtllulcnc3,6-disulplionic acid. 7- Red.

goo-ammonium o 0.- 44. 1,MliaminobcnZcnc-3-sulphomc acid... Z-arnino-8-hydroxynaphthalcnn-Gsulphonic acid 4-4, Red. 45 ,do 2-acetylamiuo-fi-hydl'oxynaphtlmlcue-7-sulphonic l A 6- Scarlet 46 do l-acctylamino-5-hydroxynapllthaltmc-7-sulpl1onic acid B 6- Red.

EXAMPLE 47 Abbreviations for the reactive components as in the table of 51.6 parts of the dyestuff obtained by diazotization of l- Example 3 Complex bound Reactive Example heavy compo- No. Ammoazo dyestuif metal nent Shade 4 1 hy ir0Xy-2-muinobcnzonc-4,iidis1llpl101licacid -r 2-mnino-fi-hydroxynaphtha1euo-7-sulpiionie C -A Ruby 7 acid. 41*........... 1-hy lroxy-2-mnincbonzonM-sulphonic acid ZZ-PtllYlami 5-hy(lmxynaphflml n sp Cu C Dm sulphouiv acid. 50 1-dinzo-E-liydt'oxy-ti-uitro-naph1.11nicncA-sulplioilicacid .Z-iuniuo-5liydmxynaphLhaImio-7- Cu A Violet SlllpllOlllt acid. Or A greenish grey.

Yellow.

Inblc 'umimlcd Complex bound Reactive Example heavy compo- No. Aminoazo dyestufl metal nent Shade 52 i-diazo-2-hydr0xy-fi-nitronaphthalenei-sulphonic acid 1-amino-8-hydroxy1iaphtha1ene 4- C B Reddish sulphonic acid. black 53 1amino2-hydroxy-fi-methylsulphonylbenzene r l-aminO-S-hYdlOxYnaphthalcne-3,6-disu1- cm A violet phonic acid.

(1 A Gray.

A G)nl-,enli(sh 1 ac G 1-arnino-2-methylbenzene-i-sulphonic acid l-amino-2-hydroxy-E-methylbenzene c B Blue" 1-amino-8-hydroxynaphthalene4 ,fi-disulphonic acid. B Grey. A Girfcnish )ac 55) The monoazo dyestufi (1-amin0-2-chlorobenzene-i-sulphonic acid 1-hydroxy-2-acetylamino o A Navy benzene) saponified at the 2-positioned acetylamino group -i 1-amino-s-hydroxynaphthalene m 3,6disulph0nic acid. 60 do Co A Gray. 61 Lamino-s-hydroxynaphthalcne4-sulphonic acid 1-l1ydroxy-2,6-diaminobenzenel-sulphonic Co A Bl k,

acid 1,3-dihydroxybcnzcne. 62 1amino-841ydroxynaphthalcnc-B,(i-disulphonic acid 1-l1ydr0xy-2,6-diarninnl)uuzenci-sul- Co A n phonic acid. 2-hydroxynaphthalenev 63 l-amino-B-hydroxynaphthaloncA-sulphonic acid l-hydroxy-ZbdiuminobcnzcurM-sulphonic Co A n acid 3-methylpyrazolone-(5).

EXAMPLE 4 moist suction-filter cake thoroughly washed with ice-water.

the procedure otherwise being the same as in Example 64; reactive dyestufis' dyeing in clear blue shades are thus obtained.

When working as indicated in Example 64, but starting from 87 parts of copper-phthalocyanine trisulfochloride and using, instead of 50 parts of the sodium salt of l,3-diaminobenzene- 4-sulfonic acid, 90 parts of the sodium salt of 4,4'-diaminodiphenyl-2,2-disulfonic acid or 90 parts of the sodium salt of 4,4'-diamino-stilbene-2,2'-disulfonic acid, reactive dyestuffs are also obtained which dye cellulose materials according to one of the processes described above in clear blue shades fast to wet processing, rubbing and light.

When starting from 4',4",4"', 4""-tetraphenyl-Cuphthalocyanine, there is obtained, afier sulfochlorination and product is precipitated at pH 1-2 by the addition of sodium "i wi th and aqflaflon chloride, filtered off with suction, washed and then re-disf F f a solved neutral in 1,000 parts of water. Asolution of 80 parts of 40 reacuve dyestflfi f dyes Feumose mammals m the 2,3 dichlomquinoxaline 6 carboxylic acid chloride in 300 presence of acid-binding agents in clear green shades fast to parts of benzene is added dropwise with intense stirring to the processmg' and blue solution and the mixture is stirred at 3040 C. while continuously neutralinng the hydrochloric acid set free by ad- EXAMPLE 65 justing the pH value of the mixture by means of sodium car- Seventy-one parts of the amino-anthraquinone dyestuff ob- Ninety-six parts (referred to 100 percent goods) of copperphthalocyanine tetrasulfochloride freshly prepared in conven- 25 tional manner by the action of chlorosulfonic acid and thionyl chloride on copper-phthalocyanine, or of the isomeric copperphthalocyanine tetmulfochloride built up from l-sulfobenzene-3,4-dicarboxylic acid via the corresponding copperphthalocyanine tetrasulfonic acid are suspended in form of the 30 moist thoroughly washed suction-filter cake in 500 parts of water and 500 parts of ice, a solution of parts of the sodium salt of l,3-diaminobenzene-4-sulfonic acid in 500 parts of water are added and the pH is adjusted to 8.5 with sodium carbonate. The suspension is stirred at room temperature for 24 35 hours and a constant pH of 8.5 is maintained by the continuous addition of sodium carbonate. The resulting condensation bonate solution to S 7. Stirring is continued until free amino tained by reaction of l-amino-4-bromo-anthraquinone-Z-sulgroups can no longer be detected. The reactive dyestuff thus fonic acid with an excess of 4,4'-diamino-diphenyl-2,2'-disulobtained having the formula fonic acid are dissolved in 700 parts of water, 27 parts of finely -(S O Na) u N n-2-3 Cu-phthalocyanine NH0 0 1:4: SOz-HN S0 Na 1 .l G 1 \N is salted out, washed and dried under vacuum at 30-40 C. It powdered 2,3-dichloroquinoxaline-o-carboxylic acid chloride is a dark blue powder dissolving in water with a blue color and are introduced at 20-30 C. with good stirring and a pH of dyes cotton and regenerated cellulose according to one of the 6-7 is maintained by the continuous addition of sodium cary i g p n ng p ss s m n i ne abOVe in Clear lu bonate solution. When amino groups can no longer be deshades of good fastness to wet processing, rubbing and light. tected, the dyestuff of the formul A similar dyestuff is obtained by using, instead of 50 parts of 0 the sodium salt of l,3-diaminobenzene-4-sulfonic acid, 40 .l parts of the sodium salt of l,4-diaminobenzene-2-sulfonic acid so Na and, instead of 80 parts of 2,3-dichloroquinoxaline-6-carboxylic acid chloride, 60 parts of 2,3-dichloroquinoxaline-6-iso SOZNQ cyanate dissolved in 300 parts of benzene and by maintaining I a pH of 7 7.5(phosphate bufi'er) while stirring the benzenic g 2,3-dichloroquinoxaline-G-isocyanate solution with the solution of the amino group-containing phthalocyanine dyestuff. N803 S Instead of 96 parts of copper-phthalocyanine tetrasulfochloride, there may also be used 87 parts (referred to 100 percent material) of the copperor nickel-phthalocyanine I trisulfochloride obtainable by the action of chlorosulfonic NH-0 C acid on copperor nickel-phthalocyanine, in the form of the N 9955 .nnlnan is salted out, washed and dried under vacuum at 40 C. The dyestulT dyes cotton and regenerated cellulose according to one of the processes indicated above in blue shades fast to wet processing, rubbing and light.

When proceeding as indicated in Example 65, but using, instead of the starting dyestuff there employed, equivalent amounts of one of the following derivatives of l-amino-4- (aminoarylamino)-anthraquinone-Z-sulfonic acid, similar dyestuffs are obtained whose blue dyeings exhibit fastness properties similar to those of the dyestuff obtained above: 1- amino-4-(4-amino-2'-sulfophenylamino)-anthraquinone-2- sulfonic acid, l-amino-4-(4-aminophenylamin0)-anthraquinone-2,6-disulfonic acid, isomer mixture of l-amino-4-(4- aminophenylamino)-anthraquinone-2,5- and-2,8-disulfonic acid, isomer mixture of l-amino-4-(4-amino-2'-sulfophenylamino)-anthraquinone-2,5- and-2,8-disulfonic acid, isomer mixture of l-amino-4-(3'-aminophenylamino)-anthraquinone-2,5- and 2,8-disulfonic acid, l-amino-4-(3'-a.minophenylamino)-anthraquinone-2,6-disulfonic acid, l-amino-4-(3'- amino-4'-sulfophenyl-amino)-anthraquinone-2-sulfonic acid. With l-amino-4-(4'-[4"-amino-2"-sulfophenyl]amino-phenyl)-anthraquinone-2,6-disulfonic acid there are obtained reactive dyestuffs dyeing bluish grey shades.

EXAMPLE 66 When proceeding as indicated in Example 47, but starting, instead of from the copper-containing aminomonoazo dyestufi there employed, from the equivalent amount of the chromium complex of the arninoazo dyestuff obtained by coupling diazotized l-amino-2-hydroxy-3-chlorobenzene-5- sulfonic acid with l-[ 3-( 3"-aminophenyl)-sulfonylimid0-sulfonyl]-phenyl-3-methyl-pyrazolone-(5), a reactive dyestuff is obtained which dyes cellulose materials according to one of the processes described above in yellow-brown shades of good fastness to wet processing, rubbing and light.

EXAMPLE 67 Into a solution of 36.5 parts of the sodium salt of l-amino-S- hydroxynaphthalene-3,6-disulfonic acid in 200 parts of water, 23 parts of finely powdered 3- or 2-monochloroquinoxaline-6- carboxylic acid chloride of b.p. l3 l39 C./0.28 mm Hg are introduced with good stirring and the mixture is stirred at 40 C. while continuously neutralizing the hydrochloric acid set free by maintaining a pH value of the mixture of 3 6; stirring is continued until free amino groups can no longer be detected, which takes about 15 20 minutes. The clear solution of the dyestuff intermediate thus obtained is coupled, with the addition of 12 parts of sodium carbonate dissolved in 100 parts of water at C. and a pH of 6.5 7.5, with 17.5 parts of diazotized 2-aminobenzene-sulfonic acid in 200 parts of water. The resultant red dyestuff has partly crystallized and is separated by the addition of 50 parts of sodium chloride. After filtering ofi with suction, washing with a dilute sodium hydrochloride solution and drying at 40-50 C. under vacuum, the dyestufi' is obtained in form of a powder easily dissolving in water with a red color and having the formula rollers to a moisture content of about lOO percent. After intermediate drying at 5060 C., the material is heated to 140 C. for 10 minutes, the dyeing thus obtained thoroughly rinsed with hot water and treated at the boiling point for 20 minutes with a solution containing 5 g of Marseille soap and 2 g of sodium carbonate per liter. After rinsing and drying, a brilliant red dyeing is obtained having very good fastness to wet processing, rubbing and light.

According to one of the other dyeing or printing processes described in Examples 1 to 3, l8 and 30, clear red shades of good fastness properties are likewise obtained on materials of cellulose or synthetic polyamides.

The 3- or 2-chloroquinoxaline-6-carboxylic acid chloride used in this example is obtained in the following way:

One mol of 3,4-diaminobenzoic acid and l mol of monochloracetic acid are boiled under reflux in a weakly ammoniacal aqueous solution for 1 hour. The clear solution is rendered strongly alkaline with sodium hydroxide solution, treated with 1.2 mol of hydrogen peroxide at room temperature and stirred for another hour at 70 C. The 2- or 3- monohydroxy quinoxaline-6-carboxylic acid is isolated by acidification, dried and boiled under reflux with 6 mols of thionyl chloride and some dimethyl formamide until hydrogen chloride no longer evolves. Afier distilling off the excess thionyl chloride the residual 2 or 3-monochloroquinoxaline-6- carboxylic acid chloride is distilled in a high vacuum.

EXAMPLE 68 When proceeding as indicated in Example 18 but adding to the aqueous suspension of the dyestuff intennediate obtained from lamino-8-hydroxynaphthalene-3,6-disulfonic acid and 2,3-dichloroquinoxaline-G-carboxylic acid chloride after the suspension was made up with Water to 400 parts, l 1.5 parts of the monosodium salt of thioglycolic acid dissolved in 50 parts of water and neutralizing the hydrochloric acid liberated at 45 C. by means of soda solution in order to keep the pH value of the mixture at 5 to 7, a thinly liquid suspension of a monochloroquinoxaline derivative is obtained afier 3 hours reaction. The product thus obtained is coupled with 17.5 parts of diazotized o-sulfanilic acid in the presence of 12 parts of soda, the dyestufl of the following constitution thus being obtainable:

s OaNa 0H NH-O o a aS s O Na It can be used for printing of cellulosic material in the presence of sodium bicarbonate or dyeing of cellulosic materials from a long bath at C. in red shades are obtained which possess good wet fastness properties and good fastness to rubbing and to light.

EXAMPLE 69 6.2 Parts of 2,3-dichloro-6aminoquinoxaline are stirred in 30 parts by volume of glacial acetic acid and then treated with 8 parts by volume of concentrated hydrochloric acid, parts of ice and 2 parts of sodium nitrite. After stirring at 0 C. for one-half hour, the amine has dissolved and diazotization is completed. The excess nitrous acid is removed and a solution of 10 parts of the sodium salt of l-(2,5'-dichloro-4-sulfophenyl)-3-methylpyrazolone-(5 in 100 parts of water is added. After neutralization with concentrated sodium hydroxide solution to pH 4 in a stirrer with good ice-cooling, the

run

the presence of soda. Clear coupling is completed. The precipitated dyestuff of the formuis filtered off, washed and dried at 45 C. under vacuum. The dyestuff dyes cellulose materials according to the process described in Example 3 in reddish yellow shades fast to light and wet processing.

EXAMPLE 70 27.5 parts of Z-methylamino-S-hydroxynaphthalene-7-sulfonic acid sodium salt are dissolved in 150 parts of water, treated with 26.5 parts of finely powdered 2,3-dichloroquinmonobromoquinoxaline-6-carboxylic acid bromide are used and the method of preparation is otherwise carried out as indicated above an orange reactive dyestufi' is obtainable which likewise dyes cotton and regenerated cellulose orange shades of dyeing properties similar to those obtainable with the corresponding 2,3-dichlor0 derivative.

In a similar manner orange to red reactive dyestufis are obtained by acylation of the aminonaphthol-sulfonic acids listed in the following table with 2,3-dichloroquinoxaline-o-carboxylic acid chloride and coupling of the resultant acylaminonaphthol-sulfonic acids with the diazo components mentioned in Column 2.

Example Shade on No. Diazo components Aminonaphtholsulphonio acid cotton 71 2-aminonaphthalenc-l,7-disulphonic acid 2-ethy1amino-fi-hydroxynnphthalene-7-sulphonic acid Orange.

72 do 2-(B-hydroxyethylamino)-5-hydroxynaphthalene- Do.

sulphonic acid.

73 do Z-amino-fi-hydroxynaphthalcne-T-sulphonic acid- Do 74- 2-amino-5-hydroxynaphthalene-l,7-disulphonic a Do 2-amino-8-hydroxynaphthalene-fi-sulphonic acid- 76 2-amino-S-hydroxynaphthalene-3,6-disulphonic ac D 77. minonaphthalene-l,5-disulphonic acid. 2-methylarnino-5-hydroxynaphthalenc-Hulphonic ac Orange. 78 do Z-ethylamino-5-hydroxynaphthalene-7-sulphonic acid Do. 79 do 2-(fll-hfidrpxyetgylamino)-5-hydroxynaphtha1ene-7- Do.

su p 01110 aci 80. d0 Z-amino-5-hydroxynaphthalenc-7-sulphonic acid D0. 81 do 2-amino-5-hydroxynaphthalene-l,7-disulphonic acid. D0. 82- do 2-amino-s-hydroxynaphthalene-6-sulph0nic acid Scarlet. 83- "do"... Z-amino-S-hydroxynaphthalene-3,6-disulphonic acid- 0. 84. -ammonaphthalene-l,5,7-tnsulphonic acid 2-arnino-5-hydroxynaphthalcne-I-sulphonic acid Orange. 85 do 2-mcthylamino-5-hydr0xynaphthalene-T-sulphonic acid.- 0. 86 do; 2-aminc-8-hydr0xynaphthslcne-fi-sulphonic acid Scarlet. 87 2-am1nobenzenesulphonic acid 2-mcthylaminob-hydroxynaphtha1ene-7-su1phonic acid Orange. 88 u 2-s(tllil-glylglrpgggit(liiylamino)-5-hydroxynaphthalene-7- D0. 89 do 2-amino-8-hydroxynaphthalcne-G-sulphonic acid Scarlet. 90. do 2-arnin0-8-hydroxynaphtha1cnc-3,6-disulphonic acid. Do. 91.. d o .Larnino-5-hydroxynaphthalene-l,7-disulphonic acid Orange. 92. 2-aminonaphthuleneq-sulphonic acid 1-amino-B-hydroxynaphthalenc-3,fi-disulphonic acld Bluish red. 93" d o l-aininO-B-hydmxynaphthnlcnc-ifi-disulphonic acid Do. 94 2-mnmonnplithulvnc-l,S-disulphonic 1-nmino-8-hydroxynnphtliaione-3,6 disulphonic acid- Do. 95 H J o t l-aniiuo-8-liydr0xynaphthnlcnn-4,6-disulphonic acid Do. (lo 1-an1in0-8-hydroxynaphthalmlc-6-sulphonic acitL. D0. !)7 innmoimplithalcnn-l,7-disulph0 c n l-amino-8-hydioxynaphthuivno-S ('Hllsulphomc I Do. il8 i 1-amino-8-hydrnxy1iaphthulcnc-4,6-disulplionic acid Do. 09.. l l'amino8-hydroxynaphthalcue-fisulphonic acitL. Do. 100. 2-ainmonaphtlialenc-l,5,7-trisulplioniu acid l-amin0-8-liydroxynaphtllalene-fi-sulphonic acid- Do. 101. 1-ainino-4-chlorbcnzcne-Z-sulphonic acid-. l-amino8-hydr0xynaphthalene-3 G-disulphonic no Do. 102... l-amino-2-mcthoxybcnzenc-S-sulphonic acid d0 Do. 103.. 1-amino-benzcne-2-carbonic acid-4-sulphonic acid D0. 104... l-am1no-4-acetyI-arninobcnzene-Z-sulphonic acid do Violet. 105 do l-amino-fi-hydroxonaphthalone-4,6-disulph0nic a d--. Bluish red.

NaOaS oxaline-6-carboxylic acid chloride and stirred at 40 C. for one-half hour while continuously neutralizing the hydrochloric acid formed by adjusting the pH to 4 6 with a total of 34 parts by volume of a 16 percent sodium carbonate solution. Acylation is completed already after 15 minutes, the pH is 6 and does not change any more.

By the addition of 200 parts of water, the partially crystallized reaction product is dissolved at C. Thirty parts of sodium bicarbonate are then added and a diazo suspension from 34 parts of the disodium salt of 2-aminonaphthalenei ,7- disulfonic acid in 200 parts of water is added dropwise at 40 C. within l5 minutes. The reactive dyestufi' immediately formed and having the formula uuu 56.8 parts of the diaminoazo dyestufi obtained by coupling of diazotized 1-amino-3-acetylaminobenzene-6-sulfonic acid with 2-aminonaphthalene-5,7-disulfonic acid in an acetic acid medium and subsequent alkaline or acidic hydrolysis of the acetylamino group, are dissolved at pH 7 in 450 parts of water. After the addition of 26.5 pans of finely powdered 2,3- dichloroquinoxaline-tS-carboxylic acid chloride, the mixture is stirred at 45 C. for about 3 hours while continuously neutralizing the hydrochloric acid set free by adjusting the pH of the reaction mixture with sodium carbonate solution to 4 6. After completion of the acylation, the resultant dyestuff of the formula is salted out, filtered ofi, re-dissolved in 4,000 parts of water at 60 C., filtered and separated from the fi formula ltrate in completely a a pure form by the addition of 400 parts of sodium chloride. The N dyestuff is dried as usual at 45 C. under vacuum. It dyes cellu- NH C C1 lose materials according to one of the processes mentioned above in fast yellowish orange shades. Na0z$ soaNa H 0H3 N 1 EXAMPLE 107 and, after filtering off, drying at 45 C. and grinding, it is a yellow powder which easily dissolves in water with a yellow color and dyes cellulose fibers according to one of the dyeing processes mentioned above,in the presence of acid-binding agents in very fast reddish yellow shades. Fast yellow shades are also obtained on wool and polyamide fibers.

Similar dyestuffs are obtained by proceeding as indicated above, but using, instead of 60 parts of 4-amino-2'- acetylaminophenyl-( l )-azo naph halene-( 2 )-3.6.8-trisulfonic acid sodium salt, corresponding quantities of the aminoazo dyestuffs obtained from the amino compounds listed in the following table in Column 2, and the coupling components given in Column 3 in conventional manner by diazotization and coupling in an acetic acid medium, and by acylating with 2,3-dichloroquinoxaline--carboxylic acid chloride.

To a neutral solution of 60 parts of the trisodium salt of the l 0 aminoazo dyestufi" obtained by coupling diazotized 2- aminonapthalene-3,6,8-trisulfonic acid with 3- acetylaminoaniline in an acetic acid medium, in 500 parts of water there are added 26.5 parts of finely powdered 2,3- dichloroquinoxaline-6-carboxylic acid chloride and the mix- 1 5 ture is stirred at C. for 6 hours, a pH value of about 6 being maintained by continuous addition of sodium hydroxide solution. The partially precipitated acylation product is completely separated at pH 6.5 by the addition of 100 parts of sodium chloride and filtered off. For purification, the reactive dyestuff thus obtained can be redissolved in 2,500 parts of water of C., clarified and separated again by salting out the warm filtrate with 350 parts of sodium chloride. The dyestuff has the Example N o.

Diazo components Coupling components Shade on cotton 1-arnino-3-methyl6-methoxybenzone Str ngly reddish yellow. -omino-3-methylbenzene Yellow. 1-a1ninonaplithalene-U-sulphonio acid Rcddish yellow. 1-a1nino-li-acetylmnino-benzene. Do. 3-aminophenylurea Do. l-arnino-3-hydroxyueetylzunino benzene.

Do. l-amino-3-nretl1yl-tmethoxybenzene Strongly reddish yellow. l-aminonuphthalene-7-sulpho1lie acid Reddish yellow.

l-znniiro-3acetylaminobenzcne Do. 3-zm1inophenyl urea Do.

l-amino-3-hydroxyaeetyl-mnino benzene. 1-an1ino-3-methyl-6-methoxybenzene 1-amino 3-methylbenzene l-aminonaphtlmlene-flsulphonie acid l-amino-3-methylbenzene l-amin9-3-methyl-6methoxybenzene. 1-amino-3-acetylaminobenzene Do. Strongly reddish yellow. Redgish yellow.

. Strongly reddish yellow.

Reddlsh yellow. 3-aminophenyl urea Do. 1-a1nino-S-hydroxyacetylaminobenzene. Do. 1-aminonophthalenc-(i-sulphonie oeid. Do. 1amino-3-aeetylaminobenzene-.. Do. l-amino-2-methoxyrmphthalene-lisulphonic uel Strongly reddish yellow l-nminonapl1thalene-6-sulpl1onie neid eddis yellow.

. ..do ellow. l-arninonaphthalene-7-sulphonie aeid.. D

1-amino-2-methoxynar)lrthaler1e-('r-sulplr0 l-methylamino3-methylbenzene 1-ethylumino-3-methylbenzene..

. N-Inetlrylaniline.

l-mnino-3-lrydroxyneetyleinil1o benzene. 1-nn1ino3-:u-otyl:nnino-(Hnethoxyhenzene. l-mnino3-neetylull|i1lo-fi-rnetllylbenzene. 1-mnino-3-1notlm|ie-sulphonylaminobenzen 5-dinrethoxym1iline...

...... N-1nethylaniline Yellowislromnge.

Reddish yellow.

.... Yellowish orange.

. o. Reddislr yellow. N-ethylanilrno... Do. N-lmtyluniline Do. N-(B-hydroxyethyD-uni Do.

. lamino-2-methoxybenzene. Strongly reddish yellow.

l-amino-s-methoxylienzene Reddish yellow. l-ethylamino-34netlioxybenzeneu Do. l-aminonoph thaleneG-sulphonic acr Do. .-dol-aminonuphthalene-7-sulpll0nic acid. Do. Z-aminonaphthalene4,6,8-trisulplronic acid l-ainino-3inethylbenzene Do.

(1 l-amino-3aoetylaminobenzene Do. l-znnino-3-1nethylbenzene Yellow. 1-aminonaphtlmlene-fi-sulphonic acid. .Do. l-amino-3-aeetylznnirrobenzene Reddlsh yellow. 3-aminophenyl urea Do. l-amino-IHlydroxyeeetylurnino benzene Do. Nanetlrylaniline Do. N-ethylaniline. Do. N-butylaniline. Do. N-(fl-hydroxyethyl D0. 1-(N-ethylzuniuo)-3metllylbenzene Do. l-aminonuphtlralene-G-sulphonie acid Do. 1-arninonaplltlmlene-7-sulphonie acid Do. 1-amino3-1nethylbe|rzene Yellow. 1-amir1o-3-aeetyla1nino benzene Do. l-mnino2-1nethoxy-5-rnetl1ylbenzene Reddisll yellow. l-ninino-Z 5-dirnetlroxybenzene.... D0. l-nn1ino-..-metlroxy-5-1nethylbenzeno Do.

/\ NHE is salted out, filtered off, washed and dried at 40-50 C. The dyestuff dyes cellulose materials according to one of the processes mentioned above in very fast ruby shades.

Dyestuffs with similar properties are obtained analogously to the working method described above from the copper complexes of the azo dyestuffs prepared from the diazo and azo components listed in the following table:

processing, to rubbing and to light and which are good dischargeable to white.

EXAMPLE 203 A fabric of cotton or staple fiber is impregnated on a foulard at 20 to C. with a solution which contains per liter g of the dyestuff described in Example I8, 100 g of urea and 20 g of soda. The fabric is squeezed off to a moisture content of l00 percent and the moist fabric then rolled up. After 4 to 24 hours storing at room temperature the fabric is rinsed in water and soaped at the boil and dried. One obtains a clear bluish red dyeing having good fastness to wet processing, to rubbing and to light.

EXAMPLE 204 A cellulose fabric is printed with a printing paste which contains per kilogram 30 g of the dyestuff described in Example 18, lOO g of urea, 300 g of water, 500 g of alginate thickening (containing g of sodium alginate per kg of thickening), 10 g of soda and 10 g of the sodium salt of 3-nitrobenzene-sulfonic acid, the printing paste being made up to l kilogram with water, and the fabric is after intermediate drying steamed in a suitable steaming apparatus at 103 to 1 15 C. for 30 seconds. After rinsing and soaping at the boil a strong bluish red print having good fastness to wet processing, rubbing and to light is thus obtainable.

EXAMPLE 205 One hundred parts of a woollen fabric are introduced at 40 C. into a dye-bath which contains in S l of water 1.5 parts of the reactive dyestufi described in Example as well as 6 parts of 30 percent acetic acid and 0.5 parts of a polyhydroxyethylated hydroxyl group-containing stearyl amine derivative. The dye-bath is heated to the boil within 30 minutes and dyeing continued at this temperature for 1 hour. The dyed fabric is then rinsed in water and dried, a brilliant orange Example Shade N0. Diazo components Coupling components on comm] 181 l-hydroxy-iZ-amino-benzcne-i-sulphonic acid 2-methylamino5-hydi'oxynaph thalcne-T-sulphonic acid" Ruby. 2-cthyl-arnino-Hrydroxynaph thalcnc-T-sulphonic acid- Do "do 2-(B-hydroxycthylamino)-5-hydroxynaphtl1alenc-7-sul- Do.

phonic acid. 2-arnin0-8-hydroXy-napl1thalene-3,6-disulplionic acitL Do. 2-amino-5-hydroxy-naphthalcne-L7-disulphonic acid. D0. Lamino-S-hydroxy-naphthulcnc-3,6-disulph0nic acid Do. .l-mcthylun1in0-5hydroxyiraphtlialenc-7-sulphoiiic ucld D0. 2-cthylon1ino5-hydroxynaphtlmlcnc-7-sulplionic acid D0. ,2-(fl-hydroxycthyl-arnino) -5 hydroxy-naph thalcnc-7-sul- D 0.

phonic acid. l-amino-8-hydroxynaplithalcnc-3,6disulfonic acid Violet. l-arnino-S-hydroxynaph thalcnc-4,6-disuli0nic acid Do. I-amindS-hydroxynaph thalene-3,6-disulionic acid D0. g 0 1-ainin0-8-hydrcxynaphtl1alcne-4,&disulfonic acid D0. 194. l-hydr'oxy -an1ino-4-acctylaminobenzcue sulfonic acid. LaminmB-hydroxynaphthalene-3,6-disulfonic acid. Bluish violet. 19.5 1-llydroxy-2-iunino-4acetylaruinobcnzenc-ti-suilonic acid 1cthoxy-8-hydroxynaphthalene-a,fi-disulfonic acid D0.

(i-positioned ncetylamiuo group subsequently saponilicd). 195 g l-amino-S-hydroxynaphthalcneQA-disulionic acid Blue. 197 l-amino-S-hydroxyriaphthalcne-2,4,6-trisulf0nic acid. Do. 198 1-11ydroxy-Z-amin0-6-acetyla e-4-sulionic acid l-arnino-S-hydroxynaph th alone-2,4-disull'onic acid D0.

. (sa unified 141 f a-h dr xy-s-nitmnaphthaIene--sulionic acid (fi-posi- 0 Do.

tinned nitro group subsequently reduced to NH:). 200 1-diazo-2)-hydi0xy-6nitr0naphtlialcnc-4-sulfo11ic acid (1'el-mnindS-hydroxynophthalenc-2,4,G-trisulfonic acid D0.

duced 201 1.hydrQxy-2-amino-G-acetylaminobenZe11e- -Slll '0ni0 aci d0 D0.

(saponified) EXA 202 shade thus being obtainable having excellent fastness to wash- The reaction product from l,3-diaminobenzene-6-sulfonic acid and 2,3-dichloroquinoxaline--carboxylic acid chloride obtained according to the method given in Example 30, is coupled in soda-alkaline medium with 40 parts of l-acetylamino- 8-hydroxynaphthalene-3,6-disulfonic acid. The dyestuff thus formed is isolated as in Example 30. It dissolves in water and dyes cellulose-containing materials,particularly textile materials of cotton and regenerated cellulose, with the aid of soda as acid-binding agent from a long liquor at 40 C. in the so-called cold pad batch process or according to thepad steam or pad dry heat fixing process (at 140 C.) bluish red shades which distinguish themselves ing, milling and light.

EXAMPLE 206 by very good fastness to wet hydrochloric acid by continuously adjusting the pH to 4 to 6 by means of aqueous soda solution. The precipitated dyestufi corresponds to the formula 22 EXAMPLE 238 52.4 Parts of the disodium salt of 4-([4"-aminophenyl]- SIOKNa amino)-2'-nitrodiphenylamine-3,4'-disulfonic acid are dis- N solved in l l of water and stirred with 26 5 arts of finel w- 4 s P Y 01 EN NTN (i fi CH3 dered 2,3-d1chloroquinoxaline-6-carboxylic acid chloride at 01 HO N 45 to 50 C. for 5 hours. The hydrochloric acid set free is continuously neutralized by adjusting the pH value of the reaction 1 mixture to 4 to 6 by means of soda. The nitro dyestufi" thus obtained corresponds to the formula Naois I NaOaS-NH-NH i l No: S OJNQ. it is filtered,again dissolved in 3 l of water at pH 6 to 7 and I5 precipitated from the filtered solution by means of sodium chloride. The dyestufi is filtered with suction and dried. A yel- NH-OC 01 low powder is thus obtainable which easily dissolves in water and which dyes cellulose-containing materials from a long \N/ 01 liquor at 40 C. or according to the so-called low-temperature pad batch process with the use f Soda as acidbinding agent It IS salted out, filtered with suction, washed and dfried. lt dyes clear yellow shades being fast to washing, rubbing and light. CFHUIOSe'COYIIammE matfvrlals the PI'eSenCe 0 a. p lf proceeding in analogous manner but using in this example vlolef brown Shades bemg fast to wet Procesbmg and to instead of the aminoazo dyestufi obtained from l-diazo-4- rubbmgnitrobenzene-Z-sulfonic acid and l-(2'-chloro-5'-sulfophen- EXAMPLE 239 yl)-3-methyl-5-pyrazolone and subsequent reduction the aminoazo dyestufis prepared from the starting components The condensation product of the sodium salt of l-amino-8- listed in the following table one likewise obtains valuable hydroxynaphthalene-3,6-disulfonic acid and 2,3- fiber-reactive dyestuffs the shade of which on cellulose-condichloroquinoxaline--carboxylic acid chloride which is obtaining textile materials is indicated below. tainable according to the method given in Example 18 is pH-vfalge o t e reaction Shade on No. Diazo components Z componen mixture cellulose 207.... l-amino+nitrobcnzcneQ-sulfonic acid (-positioned nitro- 1'(4-sultoplienyl)-3-methyl-pyrazolone-(5) 5-6 Yell group subsequently reduced to NH?). I 203 do 1-(4-sulfophenyl)-3carboxy-pyrazolonc-(5) 5-6 Rcdgish Y0 OW- 209 .do l-(3' sullophenyl)-3methyl-5-aminopyrazole 6-7 Yell 2 0. l-ainino3-acetylaminobenzcne-fi-sullonic acid (3-positioned .....do 6-7 Do.

acetylamino group subsequently saponified). 211. i-amino-3-acetylaminobenzene-fi-sulionicacid (3-positioned 1-( 9-liydr0xyetliy1)-3-methylpyrazolone-(5) 5-6 Do.

acetylamino group subsequently saponified). I 212.... 2 mols of l-aminO-S-acctylaminobcnzcnefi-sulfonic acid 1 mol of bis-pyrazolone from 4,4-bis-hydrazino-dibenzyl- 5-6 D (saponificd). 2,2-disulfonic acid and acetoacetic ethylestet'. 213 1 mo! 1-mnino-3-acetylaminobenzene-S-sulfonic acid (sa- 1-(4'suli0phcnyl)-3'caiboxy-pyraz0Ionc-(5). 5-6 Do;

onified). 214 l-a tnjno-fi-aceliylanlillOllapllLlltllOllO-3,7dlSllif0lliC acid (sa- .(l0 5-6 Reddish ponificd). yellow. 215 l-amino-2-methylbenzcnc-4,6-disulfoi1icacid Q-acctylamilio-5naphtliol-7-sulioiiicacid(sapouified) 7-8 Oran e. 21 acetylamiI10-8-naplitliol-ti-sulionic acid (saponiiicd) 7-8 Red. 217 1-amino-..-n1ethylbenzcnegfi-disulionic acid 1-021 0I'0-?;1(;Y; yittIllill0-5-llllplltllOl-7-Sl1ll0llicacid 7-8 Orange.

SilpOlll l0 21 1- minobenzene-2-sulioiiic acid l-acetylami110-8-11ydroxyuaphtlialclie-4,6-disuliouic acid 7-8 Red.

(saponiiied). 219.... 2-aminonaphthalene 3,6-disulfonic acid 1-acety1amino-8-hydroxynaphthalene-4,6disulfonic 7-8 Bluish red.

acid (saponiiied 220 2 aininonaphthalcnc-3,7-disulfonic acid ..do 74; D 221 2-amin0naphthalene4,8-disullonic acid. ..do.. 7 3 D 222. 241minonapilthal0n0-3,6-dl5llll0nic acid l-acetylam1no-8-hydroxynaphth 7-8 D0.

acid (saponified). 223.... 2-mninoiiaplithalcne-4,8disuli01iic acid 0 7-8 Do. 224.... l-aminoi-incthoxybenzcne-2-sulfonic acid 2-(N-acetyl-N-niethylamino)-5-hydroxynaphthalcnc- 7-8 Yellowish.

7sulfonic acid (saponificd). 225 (lo 2(N-acctyl-N-inethylainino)-8-hydroxynaphthalenc- 78 Red.

fi-sulfonic acid (saponified). 226.... Laminobcnzcne2-sull'onic acid 7-8 Red. 227.-.. l-aininol cnzenc 3-sulionic acid. 7-8 Red. 228.... l-aminobcnzcne-isulfonic acid- 7-8 Red. 229.-.. 1-amino-4metliylbenzcne2-sulfonic act 7-8 Red. 230.... 1-ainino-2 4-dimethy1benzene-(isulionic acid 0 7-8 Red. 231 ..do.. 2-aeetylainino-8rhydroxynapht e-6sulfonic acid 7-8 Red.

(saponifie 232 do 2-acetylamino-S-hydroxynaphthalene-3,6-disulfonic 7-8 Red.

acid (saponificd). 233--.. 4-aminoazobenzene-3,4'-disulfonic acid l-aln1110-3-acctylaminobenzene 5-6 Ycllowish brown. 234 ..do 1-amino-3-hydroxyacetylaminobenzenc 545 Do. 235. .-do.. l-amlnonaphthalene-fi-sulfonic acid... 5-6 D0. 236.. do. l-aniinonaphthalene-7-sulfonic acid.. 5-6 Do. 237 .do 1-amino-2(4'-an1ino-2sulfophenyl-(1)-azo)-8-liydroxy- 8 Black.

iiaplithalcne-3,6disulf0nic acid.

In the preceding tables the expression saponified means that an acylamino group being present in the aminoazo dyestuff is saponified, and the expression reduced means that a nitro group being present in the diazo compound is reduced after coupling, to form the aminoazo dyestuff.

diluted with 400 parts of water, and 19.5 parts of the sodium salt of l-aminobenzene-3-sulfonic acid dissolved in little water are added. The mixture is then adjusted to a pH of 2.5 to 3 with some hydrochloric acid and stirred at to C. for 4 hours. During this reaction time the pH is kept at 2.5 to 3 by After filtering with suction it is redissolved neutral in 2 l of water at 50 C. The solution is filtered and the purified dyestufl precipitated by the addition of 200 parts of common salt. The filtered product is dried and pulverized. it represents a red powder which easily dissolves in water and dyes cellulose materials in the presence of soda from a long liquor at 80 C. bluish red shades of good fastness to wet processing, to rubbing and to light.

EXAMPLE 240 26.5 Parts of finely powdered 2,3-dichloroquinoxaline-5- carboxylic acid chloride (mp 113 to 114 C.) are added with good stirring to a solution of 36.5 parts of the sodium salt of lamino-8-hydroxynaphthalene-3,6-disulfonic acid in 100 parts of water and the mixture is stirred at 20 to 40 C. while neutralizing the liberated hydrochloric acid and maintaining the pH at 4 to 6. Stirring is continued until free amino groups of the starting materials are no longer detectable. The reaction mixture is diluted with 600 pars of water, 12 parts of soda are added and the mixture is slowly treated at 5 to C. with a solution of 17.5 parts of diazotized Z-aminobenzenesulfonic acid in O parts of water. The dyestufi of the formula No. Condensed 2-chlor0pyrazine derivative 241- (2, 3-dichioro-quinoxalinyl-6)-acetylchl0ride.

Condensed 2-chloropymziuc derivative 248.- 2, agiichloro-quinoxaline-B-methyisulfonyl-ti-carbcxylic acid oridc.

C 249 2, 3-dichloro-quinoxaline-7-methoxy-ti-carboxylic acid chloride. 250. 2, 3-dichloro-quinoxaline-tiehloro-fi-suiionic acid chloride. 251 2, 3-dichloro-quinoxaline-Seyano-fi-sulionic acid chlt'ride. 252- 2-chl0ro-3-mcthoxy-quinoxaline-fi-carboxylic acid chloride.

010 C Cl EXAMPLE 255 ice; to this mixture there is added dropwise within 10 minutes the solution of 7 parts of sodium nitrite in 30 parts of water. After stirring at 0 to 5 C. for half an hour the amine has completely dissolved and the diazotization has finished. Excess nitric acid is destroyed and the diazonium salt solution filtered. It is then allowed to run with ice cooling into a solution of 18.1 parts of N,N-di-(B-hydroxyethyl)-aniline in 200 parts of water and 10 parts by volume of concentrated hydrochloric acid. After neutralizing the mineral acid with soda-lye to pH 5 to 6 the coupling is completed and the water-insoluble azo dyestuff of the formula precipitated. it is filtered with suction, washed with water and dried under vacuum at 40 to 50 C.

The dyestufi dyes from aqueous dispersion polyester fibers orange shades with very good fastness to wet processing, to sublimation and to light; synthetic polyamide fibers can be dyed in yellowish orange shades which possess very good wet fastness properties.

EXAMPLE 256 if 2,3-dichloro-6-aminoquinoxaline is diazotized as prescribed in Example 255 and the diazonium salt solution is allowed to run into a solution of 9.4 parts of phenol in 200 parts of water and parts of soda-lye, the dyestufl thus formed precipitates while buffering the reaction solution to a pH of 6 to 7. The dyestufl is filtered, washed with water and dried under vacuum at 40 to 50 C. An aqueous dispersion of the dyestufi dyes synthetic polyamide fibers reddish yellow shades possessing excellent fastness to wet processing and to light.

EXAMPLE 257 A neutral solution of 54.7 pans of the disodium salt of lamino-4-( 2 '-methyl-3 -aminophenyl )-aminoanthraq uinone- 2,5'-disulfonic acid in l ,000 parts of water are stirred at 30 C. for 4 hours with 26.5 parts of finely powdered 2,3- dichloroquinoxaline-fi-carboxylic acid chloride. The liberated hydrochloric acid is continuously neutralized by adjusting the pH of the mixture to 6.5 to 7. After the reaction is complete Mala the reactive dyestufi thus formed and having the formula NH2 1 l S O Na i i f, OaNa II v 0 NH l0 1 N on: NH-O o 01 I5 is salted out, filtered, washed and dried at 40 to 50 C. It dyes cellulosic materials for instance from long bath at 70 to 80 C. with the aid of soda as acid binding agent clear blue shades having very good fastness to wet processing, to rubbing and to light.

Anthraquinone dyestuffs of similar dyeing properties are obtained if proceeding as indicated above but using instead of the afore-mentioned water-soluble amino anthraquinone derivatives equivalent quantities of the anthraquinone sulfonic acid derivatives indicated in the following table, and acylating them with 2,3-dichloroquinoxaline-o-carboxylic acid chloride.

No. Water-soluble amino-anthraquinonc derivative 258. 1-amino-4-(3-aminophcnyl)-amino-anthraquinonc-2,5-disulfo|lie acid- 259 1-arnin0-4-(2'-chloro-3-aminopl1cnyl)amino-:1ntl1raquinonc-2,6-

disullonic acid.

260. 1-amino4-(2-rnethyl-3' -methylaminophcnyl)amino-anthraquinone-2,6-disulfonic acid.

261 1-amino-4-(4-aminopheny1)-amino-antliraquin0ne-2,6,3-tr1- sulfonic acid.

263- 1-amin04-(4-aminopheny1)-amino-anthraqum0ne2,5,3-trisulfonic acid.

264 1-amino-4-(3-aminophenyl)ammo-anthraqurnonc-2,5,4-tr1- 4 sullonic acid.

265. Vlixture of 1-aruino-4-(3-aminophenyl) -am1no-anthraqumone 2,4',5- and -2,4',8-trisulfonic acid.

The following products are after-sulfonated at 20 to 30 C. with 6% oleum:

266 l-amino-4-[4-(4-a.rninobeuzyl) -phenyl]-amino-anthraquinonc-2- sulfonic acid.

267 1-amino-4-(4-methylaminophenyl)-amino-anthraqu1none-2- sulionic acid.

268. 1-amino-t-(3-methylaminophenyl)-amino-anthraqurnone-2- sulfonic acid.

269 1-amin04-(2'-methylaminophenyl)amino-ant1iraqun1onc-2- sullonic acid.

270 1-amino-4-(7-amino-naphtha1-[2])-am1no-anthraqu11rone-2- sulfonic acid.

271... Condensation product obtained from combining} mol of cyanurlc chloride, 1 mol of 1Adiamino-anthraqu1none-2-sult'onrc acid, 1 mol of aniline-2,5disulionic acid and 1 mol ol' ethylene diamine (half partly condensed) when acylated with 2,3- d1- chloro-quinoxaline-dcarboxylic acid yields a W010i reactive dyestufi.

EXAMPLE 272 A solution of 107 pans of a mixture from equal molecular parts of copper-phthalocyanine-(3,3,3")-trisulfonic acidmono-(m-amino-p-sulfophenyl)-amide and copper-phthalocyanine-( 3,3 ,3" )-trisulfonic acid-di-( m-amino-p-sulfophenyl)-amide are made up with water to a volume of 1.3 l and adjusted to pH 6; into this solution 40 parts of finely powdered 2,3-dichloroquinoxaline-6-carboxylic acid chloride are introduced at 20 to 25 C. The temperature is increased, while stirring, for about 5 to 10 C. each hour and finally kept at 45 to 50 C. for several hours. At the same time the pH of the reaction mixture is kept at about 6. l to 6.9 by adding dropwise 3 N sodium hydroxide solution. Stirring and adjusting of the pH is continued until,on an average ,each dyestufi' molecule is provided with at least one dichloroquinoxaline carboxylic acid amide residue. The final step of the reaction can easily be detected from the amount of soda-lye consumed and from determination of free amino groups.

The 2,3-dichloroquinoxaline-6-carboxylic acid can likewise be used in form of its solution in acetone.

When the reaction has finished the dyestufi solution is heated to C. whereupon non-reacted 2,3-dichloroquinoxaline-6-carboxylic acid chloride is saponified; the hydrolized product can be separated by filtration or in other separating means. The desired dyestufi is precipitated from the filtered dyestuff solution by adding parts of common salt. It is then filtered with suction and dried in a vacuum or at atmospheric pressure at about 50 C. One obtains to 200 g of a product which still contains about 30 percent common salt. The salt can be removed by stirring the cooled dyestuff with 250 parts of water and again filtering it.

The dyestufi thus obtainable dyes cellulosic materials, particularly textiles of cotton and regenerated cellulose from a long bath in the presence of soda at 40 to 80 C., and according to the cold pad batch process or by the pad steam or pad dry heat fixing process at [40 C. turquoise shades which exhibit very good fastness to wet processing, to rubbing and to light.

The starting material used in this example can be obtained according to methods known as such, for instance by adding at 0 to 20 C. and at a pH of about 6.5 3 mols of 2,4- diaminobenzene sulfonic acid to an aqueous suspension of sulfonic acid group free copper-phthalocyanine trisulfonic acid chloride and simultaneously catalyzing the condensation reaction with 3 mols of pyridine, whereupon the aforementioned mixture of the copper phthalocyanine sulfonamides is formed.

Similar reactive dyestufis are obtainable if as a starting material a mixture is used which contains the two different copper phthalocyanine sulfonamide components in the ratio of 4 2 1. Such a mixture can be prepared from the corresponding copper phthalocyanine trisulfonic acid chloride and 2 mols of 2,4-diaminobenzene-sulfonic acid.

Instead of the given starting materials other starting compounds may be used such as those containing nickel as central atom instead of copper or the sulfonamides obtained by the afore-mentioned processes from copper-phthalocyanine-4- trisulfonic acid chloride or from phthalocyanine-3,4,4,4"'- tetrasulfonic acid chloride or from phthalocyanine-4-tetrasulfonic acid chloride; similar dyes are also obtainable if as arylene diamine sulfonic acid toluylene-diamine-(2,4)-sul fonic acid-(5), 4,4'-diaminodibenzyl-disulfonic acid-( 2,2), naphthylene diamine-( l,5 )-disulfonic acid-( 3,7) are employed. All those starting products and the methods for their preparation are known from literature. The condensation with 2,3-dichloroquinoxaline--carboxylic acid chloride follows the above prescription.

Green reactive dyestufis can be obtained if 2,3- dichloroquinoxaline-6-carboxylic acid chloride is condensed with appropriate copperand nickel-phthalocyanine intermediates such as the products obtained by polysulfochlorination of 3-tetra-(p-tolyl-mercapto)-copper-phthalocyanine by means of chlorosulfonic acid, with l,3-phenylenediamine-4- sulfonic acid or l,4-phenylenediamine-3-sulfonic acid in such a ratio that about 1 to 2 sulfochloride groups are to react with 1 mol of the phenylene diamine compound, and finally hydrolizing the remaining sulfochloride groups. In a similar manner simple or mixed amino and sulfo group-containing arylation or alkylation products of trior tetra-mercapto copperor nickel-phthalocyanine can 'be acylated at the amino groups with 2,3-dichloroquinoxaline-6carboxylic acid chloride thus yielding valuable green reactive dyestuffs.

EXAMPLE 273 if in the working method given in Example 240 33.6 parts of finely powdered N-methyl-N-(2,3-dichloroquinoxaline-6-carbonyl)-aminoacetylchloride are used instead of 26.5 parts of 2,3-dichloroquinoxaline-S-carboxylic acid chloride, and adding the acid chloride to the aqueous solution of the sodium salt of l-amino-8-hydroxynaphthelene-3,6-disulfonic acid, performing the acylation, coupling the reaction product with diazotized Z-aminobenzene-sulfonic acid, salting out filtering and drying as indicated in Example 240, the dyestuff which in the free acid state corresponds to the formula is obtained. It dyes cellulosic fibers synthetic polyamides and wool according to the preceding instructions bluish red shades of good fastness to wet processing, to rubbing and to light.

EXANIPLE 274 7L2 Parts of a dyestuff which was obtained by coupling tetrazotized 4,4'-diamino-3,3-dimethyl-diphenyl-6,6'-disulfonic acid on the one side with l-hydroxyriaphthalene-4-sulfonic acid and on the other side with phenol are dissolved at pH 7 in 200 to 300 parts of water and treated with parts of finely powdered 2,3-dichloroquinoxaline-o-sulfonic acid chloride. The mixture is thoroughly agitated and the pH value kept at 9 to 7 by continuous addition of a total of 55 parts of soda. If a sample of the dyestuff solution shows no longer a strong color change when soda solution and acetic acid is added, the formed reactive dyestuff of the formula is salted out, filtered and dried in a vacuum at to 50 C. The dyestufi' dyes wool from weakly acid to neutral bath scarlet shades which are fast to wet processing and to light.

We claim:

1. A dyestuff which in the free acid state corresponds to the formula R l l xfHal group being bonded thereto directly through a nuclear carbon the benzene-azo-benzene, the naphthalene-azo-naphthalene and the benzene-azo-pyrazolone-4 series, the

5. The dyestufi' which in the free acid state corresponds to the formula '-Cl Cl 6. The dyestuff which in the free acid state corresponds to the formula s oau 7. The dyestuff which in the free acid state corresponds to the fonnula 8. The dyestufl which in the free acid state corresponds to 5 the formula atom, R is a member selected from the group consisting of hydrogen and lower alkyl, m is an integer from 1 to 2 and Hal is a member selected from the group consisting of Cl and Br.

2. A dyestuff which in the free acid state corresponds to the formula HOgS- I 9. The dyestufi which in the free acid state corresponds to the formula 10. The dyestufl which in the free acid state corresponds to the formula 1 l. The dyestuff which in the free acid state corresponds to the formula I n: IIIHOC[ l -01 1101s I N=NT/ l \N/ 01 13. The dyestuff which in the free acid state corresponds to the formula 14. The dyestuff which in the free acid state corresponds to the formula 15. The dyestuff which in the free acid state corresponds to the fonnula 16. The dyestufi which in the free acid state corresponds to the formula 0 

2. A dyestuff which in the free acid state corresponds to the formula wherein F1 is the radical of a metal-free sulfonic acid group-containing monoazo dyestuff of the benzene-azo-naphthalene, the benzene-azo-benzene, the Naphthalene-azo-naphthalene and the benzene-azo-pyrazolone-4 series, the group being bonded thereto directly through a nuclear carbon atom and R is a member selected from the group consisting of hydrogen and lower alkyl.
 3. The dyestuff according to claim 1 wherein R is hydrogen and Ha1 is chlorine.
 4. The dyestuff which in the free acid states corresponds to the formula
 5. The dyestuff which in the free acid state corresponds to the formula
 6. The dyestuff which in the free acid state corresponds to the formula
 7. The dyestuff which in the free acid state corresponds to the formula
 8. The dyestuff which in the free acid state corresponds to the formula
 9. The dyestuff which in the free acid state corresponds to the formula
 10. The dyestuff which in the free acid state corresponds to the formula
 11. The dyestuff which in the free acid state corresponds to the formula
 12. The dyestuff which in the free acid state corresponds to the formula
 13. The dyestuff which in the free acid state corresponds to the formula
 14. The dyestuff which in the free acid state corresponds to the formula
 15. The dyestuff which in the free acid state corresponds to the formula
 16. The dyestuff which in the free acid state corresponds to the formula 